Pyridine dyestuff intermediates in a hair dyeing composition and method

ABSTRACT

Hair is dyed in a natural-looking color with a composition comprising a carrier compatible with hair in which at least one of the following compounds is dispersed in an effective amount: 2,5&#39;&#39;-DIAMINO-BIS-(3,2&#39;&#39;-PYRIDYL)AMINE, 5-HYDROXY-5&#39;&#39;-AMINO-BIS-(2,2&#39;&#39;-PYRIDYL)AMINE, 6-AMINO-PYRIDYLAMINO (2)-1,4-DIAMINOBENZENE, AND ACID SALTS, PARTICULARLY HYDROCHLORIC ACID SALTS, THEREOF.

United States Patent Lange 1 *Mar. 7, 1972 sequent to Aug. 10, 1982, hasbeen disclaimed.

[22] Filed: Mar. 11, 1968 [21] Appl. No.: 711,906

Related US. Application Data [63] Continuation-in-part of Ser. No.360,449, Apr. 16,

l964, abandoned.

[30] Foreign Application Priority Data Apr. 19, 1963 Germany ..Sch 33135[52] 11.8. CI ..8/l0.2, 8/11, 8/32 [5 l] Int. Cl. ..A6lk 7/12 [58] FieldofSearch ..260/296; 8/l0.2, 32, ll

[56] References Cited UNITED STATES PATENTS 3,200,040 8/1965 Lange ..8/10.2 X

FOREIGN PATENTS OR APPLICATIONS 461,185 2/1937 Great Britain ..260/296Primary Examiner-Albert T. Meyers Assistant Examiner-Vera C. ClarkeAttorney-Michael S. Striker [51] ABSTRACT Hair is dyed in anatural-looking color with a composition comprising acarrier compatiblewith hair in which at least one of the following compounds is dispersedin an effective amount:

2,5 '-'diamino-bis-( 3,2 '-pyridyl )amine,5-hydroxy-5-amino-bis-(2,2'-pyridyl)amine, 6-amino-pyridylamino(2)-l,4-diaminobenzene, and acid salts, particularly hydrochloric acidsalts, thereof.

21 Claims, No Drawings PYRIDINE DYESTUFF INTERMEDIATES INA HAIR DYEINGCOMPOSITION AND METHOD CROSS-REFERENCES TO RELATED APPLICATIONS Thepresent application is a continuation-in-part of my copendingapplication Ser. No. 360,449, filed Apr. 16, 1964 now abandoned for HairDyeing Composition and Method.

BACKGROUND OF THE INVENTION The present invention relates to a methodand composition for dyeing keratin-containing material, for instancefurs or living human hair and the like, and particularly for dyeinghuman hair in natural-looking colors.

It has been proposed to use for the dyeing of hair and the like dyeintermediates which may be oxidized to a dyestuff while in contact withthe hair for a period of about 30 minutes. These dyeing intermediatesmay be such which may be oxidized per se, i.e. without the presence of asecond dye intermediate, or these intermediates may belong to a groupwhich must be oxidized in the presence of another dye intermediate andof an oxidizing agent in order to give the hair dye.

Dye intermediates which alone cannot be oxidized to a hair dye aregenerally called nuancing dyes or modifiers. Such modifiers include forinstance 4-aminodiphenylamine and 4,4-diaminodiphenylamine. Thesediphenylamines will serve to give a gray or bluish gray shade tooxidation hair dyestuffs which are formed of p-diaminobenzenes. However,difficulties are encountered due to the poor water solubility of thediphenylamines and, furthermore, only a limited depth of color can beachieved in this manner.

It has also been proposed to use acetates of 4-aminodiphenylamine whichhas been substituted in the 3-position by an alkoxy group for the dyeingof human hair. However, the free base which is formed upon alkalizingthese salts is so poorly soluble in water that only a hardly visibleweak coloration is obtained.

It is an object of the present invention to provide a method andcomposition for the dyeing of human hair which in a simple andeconomical manner will result in dyeing the hair in a natural-lookingcolor.

SUMMARY OF THE INVENTION DESCRIPTION OF THE PREFERRED EMBODIMENTSSurprisingly it has been found that hair as well as otherkeratin-containing materials such as wool, pelts, furs and hornysubstances can be dyed, and particularly human hair, in anatural-looking color by being treated with a dyeing composition whichcontains one or more dyestuff intermediates selected from the groupconsisting of 2,5'-diamino-bis-(3,2'-pyridyl)amine,

S-hydroxy-S-amino-bis-(2,2'-pyridyl)amine,

6-amino-pyridylamino(2)-1,4-diaminobenzene, and acid salts thereof.

These compounds may be produced by condensation of the aminopyridinederivative with the corresponding chloropyridine or chlorobenzenederivative. The method of producing the compounds is described forinstanceon pages 105 and 1 17 of "Das Pyridin und seine Derivate by H.Maier- Bode and J. Altpeter, published by Wilhelm Knapp at Halle Thesecompounds which are used according to the present invention are muchmore easily soluble in water than the analogous diphenylaminederivatives, and thus considerably stronger and more intensive haircolors or colorations of other keratin-containing material can beobtained according to the present invention.

Furthermore, surprisingly, it has been found that the compounds whichare utilized according to the present invention are'reacted bythemselves to form a hair dye upon oxidation but that it is alsopossible to use these compounds as a shading or a nuancing agent inconnection with the well-known oxidation dye intermediates of thebenzene series and the more recently developed pyridine hair dyes.

Such oxidation dye intermediates which may be used in combination withthe bis-(pyridyDamines and pyridylarninobenzenes of the presentinvention are described, for instance, on page 504 of Cosmetic Scienceand Technology by E. Sagarin and include the following:p-phenylenediamine, p-toluylenediamine, m-phenylenecliamine,mtoluylenediamine, p-aminophenol, p-amino-N- dimethylaniline,4,4-diaminodiphenylamine, 4-aminodiphenylamine,4-amino-4'-oxydiphenylamine, m-diaminoanisole and m-diethylaminophenol.

The more recently developed pyridine dyes are described in three Germanpublished applications, DAS 1,142,045, DAS 1,141,748 and DAS 1,149,496and include the following: 2,6- diaminopyridine, 2,3-diaminopyridine,4-methoxy-2,6- diaminopyridine, 4-ethoxy-2,6-diaminopyridine, 4-methy1-2,6-diaminopyridine, 4-hydroxy-2,6-diaminopyridine, 3-hydroxy-2,6-diaminopyridine, 3-hydroxy-4-methyl-2,6- diaminopyridine,3-hydroxy-4-methoxy-2,6-diaminopyridine,6-hydroxy-4methyl-2,3-diaminopyridine, 6-methoxy-2,3- diaminopyridine,6-ethoxy-2,3-diaminopyridine, 2,5- diarninopyridine,2-dimethylamino-S-aminopyridine, 2- methylamino-S-aminopyridine,2-diethylamino-5- aminopyridine, 2-ethylamino- S-aminopyridine,2-amino-5- dimethylaminopyridine, 2-amino-5-methylaminopyridine, 2-methylamino-S-methylaminopyridine, 5,5'-diamino-bis-(2- pyridyl)amineand hydrochlorides thereof.

It is an interesting feature of the compounds which are utilizedaccording to the present invention that they may be applied not only inan alkaline me;ium but also in an acidic me;ium and that the thus-dyedhair will be light-fast, and the color will be retained even uponrepeated washing, and will not rub off, while at the same time the hairtreatment is very mild and does not harm the hair. The hair dyes formedaccording to the present invention may be used within a pH range of from1.5 to 12.0 and preferably are used within a pH range from 3.0 to 10.0.

It is a further advantage of the hair dyeing compositions and the me,hodof dyeing hair according to the present invention that the oxygen of theair suffices to develop the dye inter- Soc. Japan, 66, 61 and 62,(1946).

mediates to dyestuffs. However, it is also possible to utilize oxidizingagents whereby the time required for dyeing the hair or the like will bereduced and the color will become somewhat stronger. Thus, veryintensive colors are obtained by using, for instance, hydrogen peroxideas an oxidizing agent while, on the other hand, dyeing without oxidizingagents will avoid any damage to the hair keratin which possibly could becaused by the oxidizing agent.

These compounds which, in accordance with the present invention, areincorporated in a suitable carrier will form between 0.5 and 3 percentby-weight of the dyeing composition; however, it is also possible to dyewith preparations containing as little as 0.01 percent or as much as10.0 percent of the above compounds. The oxidation dye intermediates andthe pyridine dyes which may be combined with the dye intermediates ofthe present invention are also preferably applied within the abovepercentage ranges.

The following examples are given as illustrative only without limitingthe invention to the specific details of the examples.

EXAMPLE 1 EXAMPLE IA The cream formed according to Example I is evenlybrushed onto the hair and left in contact with the hair for 30 minutes.Thereafter, the hair is rinsed and dried. A light dull-brown color isobtained.

EXAMPLE IB 80.0 grams of the cream of Example I are mixed with 20.0 ml.of 6 percent aqueous hydrogen peroxide and thereafter applied to grayhair. After contact with the hair for 30 minutes at body temperature,rinsing and drying, the hair will have an intensive dull brown color.

EXAMPLE II A cream is produced according to Example I, utilizing,however, as dye intermediates: 2.0 grams p-toluylene-fiamino.

sulfate, 0.5 grams S-hydroxy-S'-amino-bis-(2,2'- pyridyl)aminehydrochloride.

By dyeing with the thus-obtained composition as described in Example IB,a natural-looking dark blonde color is obtained. In this case, the bis-(pyridyl)amine acts as modifier.

EXAMPLE III A cream is produced according to Example I, using, however,as the dye intermediate 3.0 grams 6-amino-pyridylamino(2)- l,4-diaminobenzene l-ICl of the formula:

Dyeing hair with the thus-formed composition in accordance with Example[8 will result in a very natural-looking light ash-brown color.

Without further analysis, the foregoing will so fully reveal the gist ofthe present invention that others can by applying current knowledgereadily adapt it for various applications without omitting featuresthat, from the standpoint of prior art, fairly constitute essentialcharacteristics of the generic or specific aspects of thisinvention and,therefore, such adaptations should and are intended to be comprehendedwithin the meaning and range of equivalence of the following claims.

What is claimed as new and desired to be protected by Letters Patent isset forth in the appended claims:

1. Composition for dyeing hair, comprising a alkaline aqueous suitablecarrier compatible with the hair to be dyed and having distributedtherethrough and dispersed therein an effective amount of at least onecompound selected from the group consisting of:

2,5'-diamino-bis-(3,2-pyridyl) amine,

5-hydroxy-5-amino-bis-(2,2'-pyridyl) amine,

6-amino-pyridylamino(2)-l,4-diaminobenzene, and acid salts thereof. 2. Acomposition as defined in claim 1, and also including an effectiveamount of an oxidizing agent suitable for application to hair.

3. A composition as defined in claim 1, and also including an effectiveamount of an additional oxidation dye inter mediate.

4. A composition as defined in claim 3, wherein said additionaloxidation dye intermediate is selected from the group consisting ofp-phenylenediamine, p-toluylenediamine, mphenylenedia'mine,m-toluylenediarnine, p-aminophenol, pamino-N-dimethylaniline,4,4-diarninodiphenylamine, 4- aminodiphenylamine,4-amino-4'-hydroxydiphenylamine, mdiaminoanisole andm-diethylaminophenol.

5. A composition as defined in claim 3, and also containing an effectiveamount of an oxidizing agent suitable for application to hair.

6. A composition as defined in claim 1, and also including at least onediaminopyridine selected from the group consisting of2,6-diaminopyridine, 2,3-diaminopyridine, 4-methoxy-2,6-diaminopyridine, 4-ethoxy-2,6-diaminopyridine, 4-methyl-2,6-diaminopyridine, 4-hydroxy-2,6-diaminopyridine, 3-hydroxy-2,o-diaminopyridine, 3-hydroxy-4-methyl-2,6- diaminopyridine,3-hydroxy-4-methoxy-2,fi-diaminopyridine,6-hydroxy-4-methyl-2,3-diaminopyridine, 6-methoxy-2,3- diaminopryidine,6-ethoxy-2,3-diamonopyridine, 2,5- diaminopyridine,2-dimethylamino-5-aminopyridine, 2- methylarnino-S-aminopyridine,2-diethylamino-5- aminopyridine, 2-ethylamino-5-aminopyridine,2-amino-5- dimethylaminopyridine, 2-amino-5-methylaminopyridine, 2-methylamino-S-methylaminopyridine and hydrochlorides thereof.

7. A composition as defined in claim 6, and also containing an effectiveamount of an oxidizing agent suitable for application to hair.

8. A composition as defined in claim ,7, wherein said oxidizing agent ishydrogen peroxide.

9. A composition as defined in claim 1, wherein said compound is presentin said carrier in an amount equal to between about 0.01 and 10 percentof the weight of said composition.

10. A composition as defined in claim 1, wherein said compound ispresent in said carrier in an amount equal to between about 0.5 and 3percent of the weight of said composition.

11. A composition as defined in claim 9, wherein said compound isselected from the group consisting of 2,5-diaminobis-(3,2"pyridyl) amineand the hydrochloride thereof.

12. A composition as defined in claim 9, wherein said compound isselected from the group consisting of 5-hydroxy-5-amino-bis-(2,2'pyridyl)amine and the hydrochloride thereof.

13. A composition as defined in claim 9, wherein said compound isselected from the group consisting of 6-aminopyridylamino(2)-l,l-diaminobenzene and the hydrochloride thereof.

14. The method of dyeing hair which comprises applying to the hair aneffective amount of the composition of claim l.

15. The method of dyeing hair which comprises applying to the hair aneffective amount of the composition of claim 2.

16. The method of dyeing hair which comprises applying to the hair aneffective amount of the composition of claim 3.

17. The method of dyeing hair which comprises applying to the hair aneffective amount of the composition of claim 4.

18. The method of dyeing hair which comprises applying to the hair aneffective amount of the composition of claim 5.

19. The method of dyeing hair which comprises applying to the hair aneffective amount of the composition of claim 6.

20. The method of dyeing hair which comprises applying to the hair aneffective amount of the composition of claim 7.

21. The method of dyeing hair which comprises applying to the hair aneffective amount of the composition of claim 9.

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2. A composition as defined in claim 1, and also including an effectiveamount of an oxidizing agent suitable for application to hair.
 3. Acomposition as defined in claim 1, and also including an effectiveamount of an additional oxidation dye intermediate.
 4. A composition asdefined in claim 3, wherein said additional oxidation dye intermediateis selected from the group consisting of p-phenylenediamine,p-toluylenediamine, m-phenylenediamine, m-toluylenediamine,p-aminophenol, p-amino-N-dimethylaniline, 4,4''-diaminodiphenylamine,4-aminodiphenylamine, 4-amino-4''-hydroxydiphenylamine, m-diaminoanisoleand m-diethylaminophenol.
 5. A composition as defined in claim 3, andalso containing an effective amount of an oxidizing agent suitable forapplication to hair.
 6. A composition as defined in claim 1, and alsoincluding at least one diaminopyridine selected from the groupconsisting of 2,6-diaminopyridine, 2,3-diaminopyridine,4-methoxy-2,6-diaminopyridine, 4-ethoxy-2,6-diaminopyridine,4-methyl-2,6-diaminopyridine, 4-hydroxy-2,6-diaminopyridine,3-hydroxy-2,6-diaminopyridine, 3-hydroxy-4-methyl-2,6-diaminopyridine,3-hydroxy-4-methoxy-2,6-diaminopyridine,6-hydroxy-4-methyl-2,3-diaminopyridine, 6-methoxy-2,3-diaminopryidine,6-ethoxy-2,3-diamonopyridine, 2,5-diaminopyridine,2-dimethylamino-5-aminopyridine, 2-methylamino-5-aminopyridine,2-diethylamino-5-aminopyridine, 2-ethylamino-5-aminopyridine,2-amino-5-dimethylaminopyridine, 2-amino-5-methylaminopyridine,2-methylamino-5-methylaminopyridine and hydrochlorides thereof.
 7. Acomposition as defined in claim 6, and also containing an effectiveamount of an oxidizing agent suitable for application to hair.
 8. Acomposition as defined in claim 7, wherein said oxidizing agent ishydrogen peroxide.
 9. A composition as defined in claim 1, wherein saidcompound is present in said carrier in an amount equal to between about0.01 and 10 percent of the weight of said composition.
 10. A compositionas defined in claim 1, wherein said compound is present in said carrierin an amount equal to between about 0.5 and 3 percent of the weight ofsaid composition.
 11. A composition as defined in claim 9, wherein saidcompound is selected from the group consisting of2,5''-diamino-bis-(3,2''-pyridyl) amine and the hydrochloride thereof.12. A composition as defined in claim 9, wherein said compound isselected from the group consisting of5-hydroxy-5''-amino-bis-(2,2''pyridyl)amine and the hydrochloridethereof.
 13. A composition as defined in claim 9, wherein said compoundis selected from the group consisting of6-amino-pyridylamino(2)-1,4-diaminobenzene and the hydrochloridethereof.
 14. The method of dyeing hair which comprises applying to thehair an effective amount of the composition of claim
 1. 15. The methodof dyeing hair which comprises applying to the hair an effective amountof the composition of claim
 2. 16. The method of dyeing hair whichcomprises applying to the hair an effective amount of the composition ofclaim
 3. 17. The method of dyeing hair which comprises applying to thehair an effective amount of the composition of claim
 4. 18. The methodof dyeing hair which comprises applying to the hair an effective amountof the composition of claim
 5. 19. The method of dyeing hair whichcomprises applying to the hair an effective amount of the composition ofclaim
 6. 20. The method of dyeing hair which comprises applyinG to thehair an effective amount of the composition of claim
 7. 21. The methodof dyeing hair which comprises applying to the hair an effective amountof the composition of claim 9.